Water varnish having an enamiel surface and insoluble after drying



forming with ammonia a metallic complex of the France April 28, 1933 f atta n (ch 134-191 This invention relates to" a: water varnish :which, afterdryingQhas a. transparent enamelsurface of very pronounced crystalline brilliancy "and whichisinsoluble. 1

The present 'appl ation is a continuation in part of my ap neauonqser; No; 716,005,- filed MaI'Ch-16, -1934.

pot tothe time or the present invention; bril ham and insoluble variiisheasuchas are suitable for automobilebodies, airplanes and the like, have been of thenitrocellulosebr.oiljvarnish types. A water varni sliwhich,afterdrying, had a brilliant surface and" was" i luble" had not been known prior to my invention, so far as I am aware.

.I have discovered .that a water varnishwhich,

after; dryin'g',ji base brilliant surface and is insoluble may bemade'fby mixing'fin an aqueous ammoniacal solut onla resinous material, a higher fatty acid which may or may not have been pre: viously"; saponified, a V metallic compound which forms a metallic. complex. with ammonia and forms a metallic resin soap and cellulose and/or methylcellulose. QAmong the resinous materials which I maypmploy are ,white resin, eManilla copal, sandarac resin, gum-lac, resinicqester with aiwweak acid, or other analogousbodies. The term fresinous material is used herein to include i not only true resins'butualso gums. .lfimayuse any .of the higher fatty acids which are saponifiabley.preferablyricinoleic acid, linoleic acid or margaric acid: The i metals which may be employed are those whose'cornpounds form metallic complexes with ammonia' an'd form metallic "resin i soaps with the resin soaps formed by thereaction or the resinous materiatwiththe higher may acid in thepresence of ammonia. Such metals are zinc, nickel, cobalt, antimony, cadmium and A n he meta s ra e th la of general formula Bivalent metal.(NI- I3)4.bivalent acid radical. An example of such general formula is zinc ammonium carbonate (Zn. (NHa) 4:.CO3)

Aqueous ammoniacal solutions of the materials 1 above referred to are stable, that is, they do not form precipitates even when kept fora long time in.- closed containersybut have the property of and insoluble coatings upon I WATER, VARNISHHAVING-ANENAMEL SUR- INSQLUBLE' AFTER'DRYING Fer-nan Frederic Schwartz, l-Paris,- France, asignor .toCela Holding S. A., Luxembur Luxemburg,a corporation No Drawing. Application ugust 31,- 1935, Se-

wrial No; 38,850.. .Renewed July 12, 1937. In.

Example I resin, such, for example, as sandarac resin, is fpulverized and then treated; in a mixer provided"withaheatingjsystemjwith a solution of ammoniacal soap and water. The ammoniacal soap employedmaybejthe ricinolate, linoleate or ,margarate of ammonia. The ammoniacal soap 'reacts with'th res'into producea resin mp5 Tothe resin soap thus produced is added an ammoniacal metallic complex. Such complex may be formed by dissolving the metallic hydioxide or carbonate of oneof the previously mentioned metals inammonia. The addition of the metallic complex results in the formation of a metallic resin soap. There is "then added to the-metallic resin soapa solution'of cellulose or methyl-cellulose. The cellulose may be employed in theformof Schweitzer liquor. I

Theproduct thus obtained is perfectly stable. It may be diluted with water without forming any precipitate. Upon drying, the loss of water and ammonia causes the metal to combine with the resin and fatty acid, forming a metallic resin soap. Likewise, upondrying, the: cellulose or methylcellulose reacts upon the metallic resin soap to leave an organo-metallic complex which is, insoluble in water, is transparent and brilliant. Thefilm of varnish becomes very hard and adheres perfectly upon a surface to which it is applied.

' Example 11 .(-a) -.-As .example of production of cellulose solution, a paper paste having pure cellulose as basis is 'macerated and dissolved in an ammo-niacal solution of copper carbonate until a completedissolution is produced; the relative proportions of the; bodies employed may be those which l-are commonly employedinthe manufacture of the welhknown, Schweitzers liquor. ,The solution thus .,obtained is intended ,to be mixed with the, resins, in a quantity which is sufiicient to 0011137: spond to the quantity of resin soap employed.

(1)) A resin soap solution is formed by dissolving 20 kg. of sandarac resin in an ammoniacal water obtained by mixing 80 kg. water,- 10 kg. ammonia and 3 kg. ricinoleic acid.

(0) Zinc carbonate is prepared by adding 6 kg. of sodium carbonate to asolution of kg. of zinc sulphate in water. The precipitated zinc carbonate is then filtered, washed and dissolved in kg. of ammonia in the presence of 10 kg. ricinoleic acid to form an ammoniacal zinc complex.

The flnal product is obtained by intimately mixing together: cupro-ammoniacal cellulose solution (a), resin solution (b), ammoniacal zinc complex The invention may be carried out by other methods than those particularly described. The varnish may be made in various ways so long as there is mixed together in aqueous ammoniacal solution a resinous material, a higher fatty acid, a metallic compound which forms a metallic complex with ammonia and forms a metallic resin soap, and cellulose or methyl-cellulose.

Cellulose and/or methyl-cellulose as suitable organic materials for use in my water varnish are specifically claimed in this application. Broader claims covering these and other organic materials are contained in a separate application.

Althouh I have given two examples of the manner in which the invention may be practiced, it is to be understood that the invention may be otherwise embodied or practiced within the scope of the following claims.

What I claim is:

l. A varnish comprising the reaction product of an ammoniacal aqueous solution containing:- a resinous material,.a higher fatty acid, a metallic compound which forms a metallic complex with ammonia and forms a metallic resin soap, and a material of the class consisting of cellulose and methyl-cellulose which reacts upon the metallic resin soap to leave upon drying an organometallic complex which is insoluble in water.

2. A varnish comprising the reaction product of an ammoniacal aqueous solution containing:- a resinous material, a higher fatty acid, a compound of a metal of the group consisting of zinc, nickel, cobalt, antimony, cadmium and tin which forms a metallic complex with ammonia and forms a metallic resinsoap, and a material of the class consisting of. cellulose and methyl-cellulose which reacts upon the metallic resin soap to leave upon drying an organo-metallic complex which is insoluble in water.

3. A varnish comprising the reaction product of an ammoniacal aqueous solution containing:- a'resin ous material, a higher fatty acid, a zinc compound which forms a zinc complex with ammonia and forms zinc resin soap, and amaterial of the class consisting of cellulose and methylcellulose, .the zinc resin soap having the property of reacting upon the cellulose or methyl-cellulose to leave upon drying an organo-zinc complex which is insoluble in water.

4. A varnish comprising the reaction product of an ammoniacal'aqueous solution containing:-

a resinous materiaL a saponified higher fatty acid,

a metallic compound which forms a metallic complex with ammonia and forms a metallic resin soap, anda material of the class consisting of cellulose and methylcellulose which reacts upon the metallic resi'n soap to leave upon drying an organo-metallic complex which is insoluble in water.

5. The process of making a varnish, which comprises mixing in an aqueous ammoniacal solution a resinous material, a higher fatty acid, a metallic compound which forms a metallic complex with ammonia and forms a metallic resin soap, and a material of, the class consisting of cellulose and methyl-cellulose and having the property of reacting upon the metallic resin soap, to leave upon drying an organo-metallic complex which is insoluble in water.

6. The process of making a varnish, which comprises mixing with a resin metallic soap in aqueous ammoniacal solution in the presence of a higher fatty acid a solution of a material of the class consisting of cellulose and methyl-cellulose which reacts upon the metallic resin soap to leave upon drying an organo-metallic complex which is insoluble in water.

7. The process of making a varnish, which comprises mixing with a resinv metallic soap in aqueous ammoniacal solution in the presence of a saponified higher fatty acid a solution of a material of the class consisting of cellulose and methyl-cellulose which reacts upon the metallic resin soap to leave upon drying an organo-metallic complex which is insoluble in water.

8. The process of making a varnish, which comprises mixing in the presence of a higher fatty acid an ammoniacal solution of resinous material obtained by dissolving resinous material in a solution of. ammoniacal soap, an ammoniacal metallic complex solution which reacts upon the resinous material to form a resin metallic soap, and an aqueous solution of a material of the class consisting of cellulose and methyl-cellulose.

9. The process of making a varnish, which comprises mixing together in the presence of a higher fatty acid an ammoniacal solution of resinous material, an ammoniacal metallic complex solution which reacts upon the resinous material and higher fatty acid to form a resin metallic soap, and an aqueous solution of a material of the class consisting of cellulose and methyl-cellulose which reacts upon metallic resin soap to leave upon drying an organo-metallic complex which is insoluble in water.

10. The process of making a varnish, which comprises mixing together in the presence of a previously saponified higher fatty acid an ammoniacal solution of. resinous material, an ammoniacal metallic complex solution which reacts upon the resinous material and saponified higher fatty acid to form a resin metallic soap, and an aqueous solution of a material of the class consisting of cellulose and methyl-cellulose which reacts'upon metallic resin soap to leave upon drying an organo-metallic complex which is insoluble'in water.

FERNAND FREDERIC SCHWARTZ. 

